EP0397637A1 - Procédé de déshydrogénation catalytique d'hydrocarbures alkylaromatiques - Google Patents
Procédé de déshydrogénation catalytique d'hydrocarbures alkylaromatiques Download PDFInfo
- Publication number
- EP0397637A1 EP0397637A1 EP90870070A EP90870070A EP0397637A1 EP 0397637 A1 EP0397637 A1 EP 0397637A1 EP 90870070 A EP90870070 A EP 90870070A EP 90870070 A EP90870070 A EP 90870070A EP 0397637 A1 EP0397637 A1 EP 0397637A1
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- European Patent Office
- Prior art keywords
- catalyst
- process according
- dehydrogenation
- hydrocarbons
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 42
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 42
- 238000006356 dehydrogenation reaction Methods 0.000 title claims description 46
- 238000000034 method Methods 0.000 title claims description 44
- 230000008569 process Effects 0.000 title claims description 41
- 230000003197 catalytic effect Effects 0.000 title claims description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 89
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 24
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 18
- 229910001882 dioxygen Inorganic materials 0.000 claims description 18
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 239000000395 magnesium oxide Substances 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
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- 230000000694 effects Effects 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052776 Thorium Inorganic materials 0.000 claims description 3
- 229910052770 Uranium Inorganic materials 0.000 claims description 3
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- 238000005470 impregnation Methods 0.000 claims description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- 238000011084 recovery Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 65
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 230000008929 regeneration Effects 0.000 description 12
- 238000011069 regeneration method Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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- 238000002347 injection Methods 0.000 description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
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- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
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- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
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- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C2521/08—Silica
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/10—Magnesium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/20—Vanadium, niobium or tantalum
- C07C2523/22—Vanadium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/86—Borosilicates; Aluminoborosilicates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention relates to a process for the catalytic dehydrogenation of hydrocarbons.
- the present invention relates to the dehydrogenation of alkylaromatic hydrocarbons to produce the corresponding alkenylaromatic hydrocarbons.
- the process of the invention uses catalytic systems of the redox type.
- Catalytic dehydrogenation of hydrocarbons has been carried out for many years and constitutes an important catalytic process in view of the increasing demand in dehydrogenated products which may be valorized under the most various forms such as high octane gasolines, plastic materials and synthetic rubbers.
- An object of the present invention is to provide an improved process for the catalytic dehydrogenation of alkylaromatic hydrocarbons in the presence of a redox catalytic system.
- Another object of the present invention is to provide an improved process for the catalytic dehydrogenation of alkylaromatic hydrocarbons in the absence of molecular oxygen.
- a further object of the present invention is to provide an improved process for the catalytic dehydrogenation of alkylaromatic hydrocarbons in the presence of a redox catalytic system, whether or not supported, and of which one or more oxidation stages show a dehydrogenating activity.
- a further object of the present invention is to provide an improved process for the dehydrogenation of alkylaromatic hydrocarbons in the presence of a redox catalytic system comprising at least a transition metal oxide, whether or not supported, taken alone or mixed with other metals or metal oxides showing a dehydrogenation activity.
- Still a further object of the present invention is to provide a continuous process for the dehydrogenation of alkylaromatic hydrocarbons in the presence of a redox catalytic system.
- Yet another object of the present invention is to provide a redox catalyst system for a continuous process for the dehydrogenation of alkylaromatic hydrocarbons, and a process for preparing said system.
- the present invention provides for a process for the catalytic dehydrogenation of alkylaromatic hydrocarbons into corresponding alkenylaromatic hydrocarbons which comprises : - contacting the hydrocarbon feedstock to be dehydrogenated under dehydrogenation conditions, in the absence of any gas containing molecular oxygen, with a catalyst consisting of at least one reducible oxide of a metal (I) selected from the group consisting of V, Cr, Mn, Fe, Co, Pb, Bi, Mo, U and Sn, supported on a material selected from clays, zeolitic materials of the metallo-silicate or metallo-alumino-phosphate type, and oxides of a metal (II) selected from Ti, Zr, Zn, Th, Mg, Ca, Ba, Si and Al, said catalyst having a dehydrogenation activity when said metal (I) has a valency such that it is not in its most reduced state, - recovering the dehydrogenated hydrocarbons, - regenerating the used catalyst, and
- the feedstock of alkylaromatic hydrocarbons to be dehydrogenated is contacted with a catalyst which has to fulfil several conditions.
- the catalyst comprises at least a reducible oxide of a metal selected from V, Or, Mn, Fe, Co, Bi, Mo, U and Sn; reducible oxides as used herein mean the hereabove metal oxides which are reduced by contact with hydrocarbons, when operating under dehydrogenation conditions.
- the metal oxide used has to have a dehydrogenating action under the reaction conditions.
- the Applicant has found that it is advantageous that these oxides be deposited on a support.
- suitable supports it may be cited the oxides of metals selected from Ti, Zr, Zn, Mg, Th, Si, Ca, Ba and Al, as well as clays and zeolitic materials of the metallo-silicate or metallo-alumino-phosphate type. Within the latter type, it may be cited the alumino-silicates, the borosilicates, silico-alumino-phosphates and other analogs.
- the supported catalysts used in the process of the invention may also comprise promoters such as alkali or alkaline-earth metals.
- the supported catalyst may be prepared according to usual methods such as absorption, precipitation or still impregnation.
- the contact between the feedstock to be dehydrogenated and the catalyst may be performed according to different ways; for instance the catalyst particles may be used in a fixed bed, or they may be used in a fluidized bed reactor wherein said particles are circulated and thereafter recovered, what implies a suitable distribution of the particles sizes.
- the catalyst is placed in a fixed bed and contacted with the feedstock of alkylaromatic hydrocarbons to be dehydrogenated, in the absence of a molecular oxygen containing gas, at a temperature comprised between about 300 and about 800°C, in order to maintain the feedstock in the vapor phase.
- a temperature comprised between about 300 and about 800°C
- the activity of the catalyst is reduced over the limits which are currently acceptable, generally a reduction of about 10% of the conversion, the feedstock is no longer contacted with the catalyst, but an air stream is passed over the catalyst bed at a temperature of from about 200°C to about 1000°C in order to regenerate said catalyst under mild conditions. This regeneration comprises at least a mild oxidation of the catalyst.
- the catalyst is regenerated the feedstock is again contacted with the catalyst.
- the catalyst particles whose sizes are comprised between about 0.02 and 0.3 mm, the catalyst being taken in its oxidized form, are circulating in the dehydrogenation reaction zone, and contacted with the feedstock to be dehydrogenated, in the absence of an oxygen containing gas, at a temperature comprised between about 300 and 800°C in order to maintain the feedstock in the vapor phase.
- the gas pressure at the outlet of the reactor is generally comprised between about 105 and 1.3 105 Pa while residence time of the feedstock in the reactor is of about 0.5 to 15 seconds, while the residence time of the catalyst is comprised between about 0.5 second and 5 minutes; the upper limit of the residence time of the catalyst depends obviously on its activity.
- the dehydrogenation reaction and the transportation of the catalyst to the regenerator are more particularly carried out in a fluidized bed reactor.
- the catalyst in the reactor effluent is separated from the hydrocarbon effluent by suitable means.
- the separated catalyst is a reduced catalyst because it is in a lower oxidation state than that of the fresh catalyst which enters the reaction zone.
- the separated catalyst is sent to a regeneration zone where it is regenerated with gaseous stream containing molecular oxygen.
- This regeneration comprises at least a mild oxidation of the catalyst.
- the temperature in the regeneration zone is most often maintained between about 200 and about 1000°C; the residence time of the catalyst in said zone is of about 5 seconds to 5 minutes, while that of the gas containing molecular oxygen is of about 1 to 30 seconds.
- the amount of gas together with the oxygen concentration must be sufficient to reoxidize the catalyst in its initial form. If this embodiment is used for the regeneration of the catalyst, then the dehydrogenation process may be carried out continuously, while it was not the case with the previous embodiment.
- catalysts of the MgO - SiO2 - V2O5 type which may also comprise promoters such as alkali or alkaline-earth metals.
- These catalysts comprise 40-60 wt % (preferably about 50 %) MgO, 20-40 wt (preferably about 30 %) SiO2, 10-30 wt % (preferably about 15 %) V2O5, and minor amounts of promoters (typically about 0.5 wt % CaO and about 1.5 wt % Na2O) and of other impurities.
- They are preferably prepared by spray-drying of an MgO/SiO2 suspension, followed by impregnation with an ammonium vanadate solution preferably also with a further amount of SiO2 as silicasol, evaporation and calcination at a temperature of from about 500°C to about 800°C.
- the process of the invention is suitable for the dehydrogenation of alkylaromatic hydrocarbons into corresponding alkenylaromatic hydrocarbons.
- the process of the invention is applied to the catalytic dehydrogenation of ethylbenzene and ethyltoluene into styrene or vinyltoluene respectively.
- the process is generally carried out at a temperature comprised between 350 and 800°C and preferably between 400 and 650°C, at a pressure comprised between 0.001 and 1 MPa, and at a hourly space velocity comprised between about 0.01 and 20.0 kg of hydrocarbon per hour and per kg of catalyst, preferably between 1 and 10.
- FIG 1 shows the dehydrogenation reaction zone 10 wherein the feedstock of hydrocarbons to be dehydrogenated enters through pipe 12 while the catalyst under its oxidized form enters through pipe 14.
- the dehydrogenated hydrocarbons are withdrawn through pipe 16 while the reduced catalyst is collected in the area 18 of the dehydrogenation reactor and transported to the top of the regeneration reactor 20.
- the gas containing molecular oxygen is introduced into pipe 22 while the reduced catalyst is introduced into pipe 24.
- the catalyst is recovered in the outlet pipe 14 and transported under its oxidized form in the dehydrogenation reactor 10.
- the feedstock of hydrocarbons to be dehydrogenated enters the dehydrogenation zone 10 through pipe 12 while the catalyst under its oxidised form enters through pipe 14.
- the reduced catalyst is separated in the area 18 of the reactor, using e.g. a nitrogen or steam flow entering through pipe 19.
- the dehydrogenated feed is withdrawn through pipe 16, while the reduced catalyst is collected into pipe 24 and transported to the top of the regeneration reactor 20.
- Gas containing molecular oxygen is introduced into reactor 20 through pipe 22 and exits through pipe 23, while the oxidized catalyst is recovered in the outlet pipe 14 and recycled into the dehydrogenation reactor 10.
- the process of the present invention shows many advantages with respect to the usual processes and particularly it enables to avoid drastically the formation of oxygenated products, due to the fact that the presence of molecular oxygen is excluded. Moreover, hydrogen is eliminated upon its formation, which enables to displace the equilibrium of the reaction and to run at less high temperatures.
- Another non-negligible advantage of the process of the invention resides in the fact that it allows to work with quasi isothermal reactors at a less high temperature, while with the prior processes it was practically necessary to work under adiabatic conditions.
- magnesium oxide powder 30 g were homogeneized into 200 ml of water at 90°C during 1 hour. The metavanadate solution was then added, and the resulting mixture was homogeneized at 90°C for a further hour.
- the mixture temperature was then raised to 120°C and the excess water was evaporated during 18 hours under a nitrogen flow.
- the resulting solid catalyst was calcined at 600°C during 4 hours and pelletized.
- the pellets were ground and sieved to give a V2O5-type catalyst supported on magnesium oxide.
- Ethylbenzene was passed in a pulse microreactor over 500 mg catalyst (as obtained from A) at a temperature of 505°C, under atmospheric pressure, the amount of ethylbenzene being of 3.6 mg per pulse.
- This comparative example shows that a higher yield is obtained by the process of the invention, at lower temperatures and without having to add a diluent.
- the solid was filtered off and dried at 110°C during 18 hours.
- the catalyst was then placed in an oven, the temperature being increased at a rate of 30°C/h up to 600°C and maintained at 600°C during 10 hours.
- the resulting catalyst was ground and sieved.
- Ethylbenzene was passed in a pulse microreactor over 500 mg catalyst (as obtained from A) at a temperature of 505°C, under atmospheric pressure, the amount of ethylbenzene being of 3.6 mg per pulse.
- the powder fraction between 0.04 and 0.15 mm was separated by sieving.
- the resulting mixture was introduced into a rotating flask kept in an oil bath and homogenised at 90°C during 15 minutes. The temperature of the oil bath was then raised to 120°C to dry the mixture maintained at that temperature and under slight nitrogen flushing for 18 hours.
- the powder then obtained was sieved to retain particles between 0.04 and 0.15 mm and placed in an oven.
- the oven temperature was raised at a rate of 60°C/hour up to 600°C and kept at that temperature for 4 hours.
- a catalyst was obtained, which was sieved to retain the particles between 0.04 and 0.15 mm. It contained 15.5 wt % of vanadium (expressed as V2O5), 30 % wt % of silicon (espressed as SiO2), 1.5 wt % of sodium (expressed as Na2O), and 0.45 wt % of calcium (expressed as CaO).
- the catalyst had the following physical properties : - apparent packing density : 0.69 g/ml (ASTM D-4164-82) - apparent bulk density : 0.58 g/ml (UOP standard method M.294-54T) - surface area by BET technique (N2 adsorption) - calcined at 500°C in air : 88 m2/g - calcined at 120°C in vacuum : 53 m2/g - volume of pores ⁇ 100 nm : 0.27 ml/g (nitrogen desorption) - attrition loss (air jet velocity of 7.07 1/min under standard conditions) - from 0 to 5 hours : about 3.4 wt % - from 5 to 25 hours . about 1.8 wt %
- Ethylbenzene was passed in a pulse reactor over 500 mg catalyst (as obtained from A) at a temperature of 500°C and under atmospheric pressure, the amount of ethylbenzene being of 2 mg per pulse.
- Ethylbenzene injections were continued until the conversion was reduced by about 10 % with regard to its initial value. The ethylbenzene injections were then stopped and the catalyst was regenerated by passing thereon air pulses at a temperature of 500°C.
- a fluidized bed reactor was used, under the following temperature conditions (described by reference to Figure 2) : - reactor (10) 500°C - regeneration (20) 500°C - stripper (18) 500°C - catalyst return (14) 520°C - feed preheater 150°C - feed entrance (12) 370°C
- the weight hourly space velocity was of 3.4.
- the catalyst used was prepared as described in part A of example 3 and calcined at 550°C immediately before use.
- the products (16 in Figure 2) comprised 0.57 mol/h of styrene and 0.40 mol/h of unreacted ethylbenzene, corresponding to : - ethylbenzene conversion 63.04 mol % - styrene selectivity 83.80 mol % - yield 52.83 mol %
- Ethylbenzene was passed in a pulse microreactor over 500 mg catalyst at a temperature of 500°C, under atmospheric pressure, the amount of ethylbenzene being of 2.1 mg per pulse, and the contact time being of about 1.3 seconds.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE8900512 | 1989-05-12 | ||
BE8900512A BE1004205A4 (fr) | 1989-05-12 | 1989-05-12 | Procede de deshydrogenation catalytique d'hydrocarbures alkylaromatiques. |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0397637A1 true EP0397637A1 (fr) | 1990-11-14 |
EP0397637B1 EP0397637B1 (fr) | 1996-06-19 |
Family
ID=3884156
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90870070A Expired - Lifetime EP0397637B1 (fr) | 1989-05-12 | 1990-05-14 | Procédé de déshydrogénation catalytique d'hydrocarbures alkylaromatiques |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0397637B1 (fr) |
AT (1) | ATE139518T1 (fr) |
BE (1) | BE1004205A4 (fr) |
DE (1) | DE69027480T2 (fr) |
DK (1) | DK0397637T3 (fr) |
ES (1) | ES2089007T3 (fr) |
GR (1) | GR3021051T3 (fr) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0482276A1 (fr) * | 1990-10-22 | 1992-04-29 | Fina Research S.A. | Procédé de déshydrogénation catalytique d'hydrocarbures alkylaromatiques |
EP0524035A1 (fr) * | 1991-06-17 | 1993-01-20 | Institut De Catalyse Du Departement Siberien De L'academie Des Sciences De Russie | Catalyseur et procédé de traitement de gaz contenant des composés soufrés |
NL1001349C2 (nl) * | 1994-10-12 | 1997-09-12 | Basf Ag | Werkwijze voor de katalytische oxidatieve dehydrogenering van alkylaromaten en paraffinen. |
US5691262A (en) * | 1994-10-18 | 1997-11-25 | Basf Aktiengesellschaft | Regeneration of catalysts used in oxidative dehydrogenation of alkylaromatics and paraffins |
US5902918A (en) * | 1994-07-07 | 1999-05-11 | Basf Aktiengesellschaft | Catalyst and catalytic oxidative dehydrogenation of alkylaromatics and paraffins |
US6521808B1 (en) * | 2000-02-17 | 2003-02-18 | The Ohio State University | Preparation and use of a catalyst for the oxidative dehydrogenation of lower alkanes |
WO2007111997A3 (fr) * | 2006-03-23 | 2008-01-24 | Velocys Inc | Procédé de fabrication de styrène utilisant une technologie de traitement par microcanaux |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR827068A (fr) * | 1936-10-15 | 1938-04-15 | Universal Oil Prod Co | Procédé de déshydrogénation des hydrocarbures aliphatiques |
GB840082A (en) * | 1958-01-10 | 1960-07-06 | Bataafsche Petroleum | A process for the preparation of diolefins by dehydrogenation of mono-olefins |
US3118007A (en) * | 1956-09-24 | 1964-01-14 | Bayer Ag | Dehydrogenation of hydrocarbons |
US4607129A (en) * | 1985-06-10 | 1986-08-19 | Phillips Petroleum Company | Catalytic dehydrocyclization and dehydrogenation of hydrocarbons |
US4644089A (en) * | 1986-07-10 | 1987-02-17 | Phillips Petroleum Company | Catalytic reforming of hydrocarbons |
-
1989
- 1989-05-12 BE BE8900512A patent/BE1004205A4/fr not_active IP Right Cessation
-
1990
- 1990-05-14 ES ES90870070T patent/ES2089007T3/es not_active Expired - Lifetime
- 1990-05-14 DE DE69027480T patent/DE69027480T2/de not_active Expired - Lifetime
- 1990-05-14 AT AT90870070T patent/ATE139518T1/de not_active IP Right Cessation
- 1990-05-14 DK DK90870070.1T patent/DK0397637T3/da active
- 1990-05-14 EP EP90870070A patent/EP0397637B1/fr not_active Expired - Lifetime
-
1996
- 1996-09-16 GR GR960402419T patent/GR3021051T3/el unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR827068A (fr) * | 1936-10-15 | 1938-04-15 | Universal Oil Prod Co | Procédé de déshydrogénation des hydrocarbures aliphatiques |
US3118007A (en) * | 1956-09-24 | 1964-01-14 | Bayer Ag | Dehydrogenation of hydrocarbons |
GB840082A (en) * | 1958-01-10 | 1960-07-06 | Bataafsche Petroleum | A process for the preparation of diolefins by dehydrogenation of mono-olefins |
US4607129A (en) * | 1985-06-10 | 1986-08-19 | Phillips Petroleum Company | Catalytic dehydrocyclization and dehydrogenation of hydrocarbons |
US4644089A (en) * | 1986-07-10 | 1987-02-17 | Phillips Petroleum Company | Catalytic reforming of hydrocarbons |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0482276A1 (fr) * | 1990-10-22 | 1992-04-29 | Fina Research S.A. | Procédé de déshydrogénation catalytique d'hydrocarbures alkylaromatiques |
EP0524035A1 (fr) * | 1991-06-17 | 1993-01-20 | Institut De Catalyse Du Departement Siberien De L'academie Des Sciences De Russie | Catalyseur et procédé de traitement de gaz contenant des composés soufrés |
US5902918A (en) * | 1994-07-07 | 1999-05-11 | Basf Aktiengesellschaft | Catalyst and catalytic oxidative dehydrogenation of alkylaromatics and paraffins |
NL1001349C2 (nl) * | 1994-10-12 | 1997-09-12 | Basf Ag | Werkwijze voor de katalytische oxidatieve dehydrogenering van alkylaromaten en paraffinen. |
US5780700A (en) * | 1994-10-12 | 1998-07-14 | Basf Aktiengesellschaft | Catalytic oxidative dehydrogenation of alkylaromatics and paraffins |
US5691262A (en) * | 1994-10-18 | 1997-11-25 | Basf Aktiengesellschaft | Regeneration of catalysts used in oxidative dehydrogenation of alkylaromatics and paraffins |
US6521808B1 (en) * | 2000-02-17 | 2003-02-18 | The Ohio State University | Preparation and use of a catalyst for the oxidative dehydrogenation of lower alkanes |
WO2007111997A3 (fr) * | 2006-03-23 | 2008-01-24 | Velocys Inc | Procédé de fabrication de styrène utilisant une technologie de traitement par microcanaux |
US7847138B2 (en) | 2006-03-23 | 2010-12-07 | Velocys, Inc. | Process for making styrene using mircochannel process technology |
Also Published As
Publication number | Publication date |
---|---|
ATE139518T1 (de) | 1996-07-15 |
BE1004205A4 (fr) | 1992-10-13 |
DE69027480D1 (de) | 1996-07-25 |
GR3021051T3 (en) | 1996-12-31 |
DE69027480T2 (de) | 1996-11-07 |
DK0397637T3 (da) | 1996-08-05 |
EP0397637B1 (fr) | 1996-06-19 |
ES2089007T3 (es) | 1996-10-01 |
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